WO2022098009A1 - Dehydrogenation catalyst for preparing olefin from alkane gas and method for producing same - Google Patents

Dehydrogenation catalyst for preparing olefin from alkane gas and method for producing same Download PDF

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WO2022098009A1
WO2022098009A1 PCT/KR2021/015488 KR2021015488W WO2022098009A1 WO 2022098009 A1 WO2022098009 A1 WO 2022098009A1 KR 2021015488 W KR2021015488 W KR 2021015488W WO 2022098009 A1 WO2022098009 A1 WO 2022098009A1
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catalyst
boron
alumina
producing
reaction
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PCT/KR2021/015488
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French (fr)
Korean (ko)
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박대성
박하원
송창열
박용기
최원춘
홍웅기
박덕수
이미영
신해빈
박상현
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에스케이가스 주식회사
한국화학연구원
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Priority to CN202180073867.8A priority Critical patent/CN116457091A/en
Priority to US18/032,990 priority patent/US20230381749A1/en
Publication of WO2022098009A1 publication Critical patent/WO2022098009A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—
    • B01J35/30—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst for producing olefins with improved selectivity and conversion compared to the prior art for producing olefins from alkane gases such as ethane, propane, and butane, and a method for producing the same.
  • Olefins such as ethylene and propylene are widely used in the petrochemical industry. Typically, these olefins are obtained in the pyrolysis process of naphtha. However, as shale gas production increased and the price competitiveness of gas raw materials improved compared to naphtha, the ethane pyrolysis process rapidly increased. As a result, ethylene supply increased while propylene production slowed down, resulting in an imbalance in propylene supply and demand. Therefore, “On purpose propylene” for propylene supply and demand control - special purpose propylene manufacturing technology is spreading, and propylene production through the dehydrogenation process of lower hydrocarbons using a catalyst is required as an important technology.
  • the fluidized bed reactor is a process in which propane and a catalyst are injected into the fluidized bed reactor together at a very high speed to react, and then the catalyst is fed into the regeneration section and the product goes into the separation section.
  • the goal of the conventionally developed FPDH process is to set the residence time of the catalyst to 10 seconds or less.
  • the residence time of the catalyst is short, the injection rate of the propane supply is also fast, and the catalyst is immediately regenerated and participates in the reaction again. Therefore, when developed as a commercial process, propylene production is significantly increased compared to the fixed bed process.
  • propane dehydrogenation process technologies are based on noble metal catalysts or discontinuous processes, so propylene They are having trouble running production.
  • the propane dehydrogenation reaction has a thermodynamic limitation on the propane conversion rate due to the reversible reaction by hydrogen. Hydrogen is being converted to water.
  • catalysts most commonly used as PDH catalysts include Pt-Sn, VOx, and CrOx catalysts.
  • the CrOx catalyst is very good in terms of propane conversion rate and selectivity, its use is limited due to problems such as environmental pollution and human harm, and difficulties in controlling the oxidation reaction in the initial stage of the reaction.
  • the platinum catalyst has excellent selectivity, but is expensive, and the coke generation rate is very high, so precise control is required.
  • the intrinsic activity of the catalyst varies according to the combination of Sn and other metals, which is a co-catalyst component, and the platinum catalyst is also continuously required to develop a new multi-component catalyst due to the increase in the environmental hazard of Sn.
  • the present inventors have developed a catalyst for olefin production and a method for preparing the same, which at the same time have excellent catalyst conversion and selectivity compared to the prior art by introducing a new catalyst through continuous research.
  • Patent Document 1 Korea Patent Publication No. 2018-0079178
  • Patent Document 2 International Patent Publication WO2016/13561
  • a metal active component is supported on an alumina carrier containing boron.
  • the boron is preferably supported in an amount of 0.1 to 2% by weight based on the weight of alumina.
  • the boron is supported in an amount of 0.5 to 2% by weight based on the weight of the carrier.
  • the metal active component essentially contains cobalt.
  • the cobalt is preferably supported in an amount of 1 to 5% by weight based on the weight of alumina.
  • the metal active component further comprises platinum.
  • the platinum is preferably supported in an amount of 0.001 to 0.05 wt % based on the weight of alumina.
  • the boron-alumina carrier is preferably calcined at 400 to 600 °C.
  • Another aspect of the present invention is to provide a process for the production of continuous reaction-regenerated olefins comprising a catalyst for the production of olefins from an alkane gas produced according to the present invention.
  • the reaction temperature is preferably 560 to 640°C.
  • the flow rate (WHSV) of alkane as a raw material is 4 to 16 h -1 .
  • the catalyst for producing olefins from alkane gases such as ethane, propane, butane, and the like according to the present invention and a method for producing the same have excellent conversion and selectivity, so they are effective for both a fixed bed reactor and a fluidized bed reactor, but in particular, the FPDH process that has not been commercially realized in the prior art. make realization possible.
  • the catalyst according to the present invention has a high conversion rate and selectivity by significantly improving catalyst deactivation by coke deposition compared to conventional catalysts.
  • Figure 2 is a schematic diagram comparing the PDH activity experimental results of 4Co/Al 2 O 3 and 4Co-0.7B/Al 2 O 3 catalysts.
  • Figure 4 schematically shows the catalyst image after 1 minute PDH reaction of the 4Co-0.01Pt-x%B catalyst.
  • 5 is a schematic view comparing the experimental results of the PDH initial activity of the Co-Pt catalyst and the Co-Pt-B catalyst.
  • a metal active component is supported on an alumina carrier containing boron.
  • a metal active component is supported on an alumina carrier containing boron.
  • the alumina carrier preferably has a ⁇ to ⁇ phase at a manufacturing temperature of 550 to 850° C. above the dehydrogenation reaction temperature, and has a surface area of 80 to 300 m 2 /g in this range.
  • the carrier is prepared at a temperature lower than the dehydrogenation reaction temperature, thermal deformation of the catalyst may occur during the dehydrogenation reaction. It inhibits mass transfer for catalytic activity.
  • WHSV 4 h-1 condition which is a 4 times slower reaction, a conversion rate of 25% or more was shown, and the production rate of methane and ethylene was higher than propylene production due to cracking, which is a side reaction.
  • cobalt is preferable to obtain high selectivity in the very early stage of the reaction within seconds, which is characteristic of the FPDH process, and furthermore, the conversion rate is improved while maintaining the high selectivity properties of the cobalt-based catalyst. It is preferable to add platinum to make it.
  • the cobalt is preferably supported in an amount of 1 to 5% by weight based on the weight of alumina. Catalyst amounts outside the above range are outside the commercially applicable range for FPDH. In addition, since a crystalline oxide is formed when the catalyst amount is large, it is negative as a dehydrogenation catalyst. Furthermore, when the amount of catalyst is increased beyond the above range, the yield is significantly reduced.
  • the cobalt catalyst shows the highest selectivity, and platinum seems to contribute the most to the conversion. Therefore, it is estimated that the platinum catalyst compensates for the low conversion rate of the cobalt catalyst with high selectivity.
  • the platinum supported at 0.001 to 0.05 wt % relative to the weight of alumina is the most suitable catalyst for application to the fast circulating fluidized bed process. there is.
  • the catalyst is preferably calcined at 700°C to 900°C.
  • the catalyst phase changes depending on the calcination temperature. Outside the above temperature range, it is not preferable as a dehydrogenation catalyst because it mainly causes a redox reaction because it forms a nano-sized crystal phase.
  • the boron-alumina carrier is preferably calcined at 400 to 600 °C. In order to use it as a carrier, it is preferable to maintain a large specific surface area, and when the temperature is higher than the above temperature range, the phase of the alumina carrier changes and the surface area decreases, and crystallization may proceed.
  • the catalyst synthesized by the sol-gel method and the precipitation method which are expected to have high crystallinity, is not preferable because the production of CO 2 by oxidation reaction rather than dehydrogenation reaction is predominant.
  • a medium pore catalyst by EISA method a synthesis method with an increased alumina ratio, or a catalyst synthesized by a precipitation method on an alumina solid slurry, the acid point of the alumina support is appropriately controlled, thereby increasing the selectivity of the dehydrogenation reaction. .
  • Another aspect of the present invention is to provide a process for the production of continuous reaction-regenerated olefins comprising a catalyst for the production of olefins from an alkane gas produced according to the present invention. More preferably, propylene is produced from propane.
  • the reaction temperature is preferably 560 to 640°C. Since the dehydrogenation reaction (PDH) is an equilibrium reaction, a high reaction temperature is required. However, side-reactions occur rapidly from 640°C or higher, and at the same time, by-products increase due to thermal reaction (non-catalyst) caused by high temperature. Therefore, in order to minimize the decrease in selectivity, a temperature higher than that is not preferable.
  • PDH dehydrogenation reaction
  • regeneration is required to remove coke deposition during the reaction. Since the reaction temperature and the temperature of the regeneration unit are mutually dependent, the regeneration unit is set at a temperature approximately 20-30°C higher than the reaction temperature. Therefore, in the case of a reaction at 560°C, the coke is removed from the regeneration unit at about 590°C. In a temperature range lower than this, it is difficult to regenerate the catalyst through rapid coking.
  • the flow rate (WHSV) of alkane as a raw material is 4 to 16 h -1 . More preferably, it is 12-16 h -1 .
  • the catalyst circulates smoothly and can have a fast residence time (RT).
  • Boric acid was used as a boron precursor for preparing the boron oxide-alumina carrier.
  • methanol was prepared in an amount equal to the pore volume of alumina.
  • H 3 BO 3 boric acid
  • B boron
  • the prepared metal oxide solution was added to alumina, impregnated by incipient wetness impregnation, and the temperature was raised at a rate of 2° C. per minute, and then calcined at a firing temperature of 500° C. for 6 hours to prepare a boron oxide-alumina carrier. did.
  • the prepared metal oxide solution was added to the prepared boron oxide-alumina, impregnated by incipient wetness impregnation, dried at 50 to 75° C. for 12 hours, and then heated at a temperature increase rate of 1° C. per minute.
  • Each of the cobalt/boron oxide-alumina catalysts was prepared by calcination at a calcination temperature of 700° C. to 900° C. for 6 hours.
  • the metal oxide solution water was prepared in an amount equal to the alumina pore volume.
  • Co(NO 3 ) 2 6H 2 O cobalt nitrate hexahydrate
  • H 2 PtCl 6 containing 0 to 200ppm (0 to 0.02% by weight) of platinum xH 2 O (chloroplatinic acid) was co-impregnation to prepare a cobalt-platinum oxide solution.
  • the prepared metal oxide solution was added to the prepared boron oxide-alumina and impregnated by incipient wetness impregnation, dried at 50 to 75° C. for 12 hours, and then heated at a temperature increase rate of 1° C. per minute. After calcining at a calcination temperature of 700° C. to 900° C. for 6 hours, each cobalt-platinum/boron oxide-alumina catalyst was prepared.
  • the reaction and regeneration temperature of 10 °C per minute is increased in an inert gas nitrogen gas atmosphere to 600 °C.
  • the temperature rise rate was reached.
  • a continuous reaction regeneration experiment was performed. After flowing into the reactor at 100 mL/min nitrogen for 5 minutes, reduction was performed with a 50 mL/min 50% propane/50% nitrogen mixed gas for 30 seconds. After flowing into the reactor with nitrogen for 5 minutes again, the regeneration process was performed in an air atmosphere of 100 mL/min for 9 minutes and 30 seconds. This was used as one reaction regeneration experiment, and continuous regeneration was performed 1 to 1000 times.
  • the reaction and regeneration temperature is 600° C. reached. After that, it was reduced with a mixed gas of 105 mL/min 50% propane/50% nitrogen for 16 seconds, and the regeneration process was performed in an air atmosphere of 30 mL/min. Next, after removing oxygen adsorbed to the reactor and the catalyst for 20 minutes using helium gas, a 50% propane/nitrogen mixed gas was injected at a flow rate of 105 mL/min, and the reaction was performed with a WHSV of 16h -1 . The reaction result was collected every second in the 16-port valve and analyzed by gas chromatography.
  • the propylene selectivity increased continuously.
  • the selectivity of the 4Co-0.01Pt catalyst was about 95%, but the catalyst in which boron was additionally supported in an amount of 0.7 to 2 wt% showed a selectivity of 99% or more to propylene.
  • the propane conversion rate was slightly decreased from 47% to 43% when 0.2 wt% of boron was supported, but it was found that it increased to 53% when the boron content was increased to 0.5 to 2 wt%. Afterwards, as a larger amount of boron was loaded, the conversion rate was gradually decreased.
  • the PDH reaction activity of the catalyst to which 0.7 wt% of boron was added and the catalyst not to which boron was added was compared.
  • the reaction is carried out at the same temperature of 600 °C, and the flow rate is WHSV: 4 h-1 and 16h-1, and The results of simultaneous comparison of catalysts after steam treatment are shown in FIG. 4 .
  • FIG. 6 shows the results of the activity experiment at the flow rate WHSV 16 h-1 of the Co-Pt-B catalyst according to the content of boron. It was found that all of the catalysts including boron significantly improved conversion and selectivity.
  • FIG. 7 shows a comparison of the results of continuous reaction-regeneration and recycle reaction activity of the 4Co-0.01Pt/Al 2 O 3 catalyst and the 4Co-0.01Pt-0.7B/Al 2 O 3 catalyst.
  • the amount of platinum required in the FPDH process is excellent even in an amount that is extremely small compared to the amount required in the moving bed type process, and the propylene selectivity is also greatly improved due to the introduction of cobalt and boron.
  • the present invention relates to a catalyst for producing olefins with improved selectivity and conversion compared to the prior art for producing olefins from alkane gases such as ethane, propane, and butane, and a method for producing the same.

Abstract

The present invention provides a catalyst for preparing an olefin and a method for producing same, wherein the catalyst is eco-friendly, and has an excellent conversion rate and selectivity compared with conventional catalysts by significant alleviation of catalyst inactivation due to coke deposition. The catalyst for preparing an olefin according to the present invention includes cobalt and platinum supported on alumina modified with boron. The catalyst for preparing an olefin and the method for producing same according to the present invention are effective in both an immobilized bed reactor and a fluidized bed reactor, and especially enables the realization of a FPDH process that was not commercially realized in the prior art.

Description

알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매 및 그 제조방법Dehydrogenation catalyst for producing olefin from alkane gas and method for producing the same
본 발명은 에탄, 프로판, 부탄 등 알칸족 가스로부터 올레핀을 제조하는데, 종래 기술에 비해 선택도 및 전환율이 향상된 올레핀 제조용 촉매 및 그 제조방법에 관한 것이다.The present invention relates to a catalyst for producing olefins with improved selectivity and conversion compared to the prior art for producing olefins from alkane gases such as ethane, propane, and butane, and a method for producing the same.
에틸렌, 프로필렌과 같은 올레핀은 석유화학산업에 있어서 널리 사용되고 있다. 일반적으로 이러한 올레핀은 나프타의 열분해 공정에서 얻어진다. 그러나 셰일가스 생산량의 급증과 가스원료의 가격 경쟁력이 나프타에 비해 좋아지면서 에탄 열분해 공정이 급증하였다. 이에 따라 에틸렌 공급은 증가한 반면 상대적으로 프로필렌 생산이 둔화되면서 프로필렌의 수급 불균형이 나타나고 있다. 따라서 프로필렌 수급조절을 위한 “On purpose propylene” - 프로필렌 특수목적 제조 기술이 확산되고 있고, 촉매를 이용한 저급 탄화수소의 탈수소 공정을 통한 프로필렌 생산이 중요한 기술로 요구되고 있다.Olefins such as ethylene and propylene are widely used in the petrochemical industry. Typically, these olefins are obtained in the pyrolysis process of naphtha. However, as shale gas production increased and the price competitiveness of gas raw materials improved compared to naphtha, the ethane pyrolysis process rapidly increased. As a result, ethylene supply increased while propylene production slowed down, resulting in an imbalance in propylene supply and demand. Therefore, “On purpose propylene” for propylene supply and demand control - special purpose propylene manufacturing technology is spreading, and propylene production through the dehydrogenation process of lower hydrocarbons using a catalyst is required as an important technology.
기존의 PDH(Propane dehydrogenation) 상업용 공정은 고정층 반응기 및 무빙베드 반응기가 대표적이다.Conventional propane dehydrogenation (PDH) commercial processes are representative of fixed bed reactors and moving bed reactors.
이에 반해, 고속유동층 (이하 유동층) 반응기를 이용하는 PDH 기술(FPDH, Fast-fluidized Propane dehydrogenation)은 현재까지 상용화 사례가 전무하다.On the other hand, fast-fluidized propane dehydrogenation (FPDH) technology using a high-speed fluidized bed (hereinafter referred to as fluidized bed) reactor has not been commercialized until now.
상기 고정층 반응기와 유동층 반응기의 가장 큰 차이점은 촉매와 반응물 (프로판)의 접촉시간이다. 즉, 유동층 반응기는 매우 빠른 속도로 프로판과 촉매를 함께 유동층 반응기로 주입하여 반응을 시킨 후, 촉매는 재생부로, 생성물은 분리부로 들어가는 공정이다. The biggest difference between the fixed bed reactor and the fluidized bed reactor is the contact time between the catalyst and the reactant (propane). That is, the fluidized bed reactor is a process in which propane and a catalyst are injected into the fluidized bed reactor together at a very high speed to react, and then the catalyst is fed into the regeneration section and the product goes into the separation section.
종래 개발중인 FPDH 공정의 목표는 촉매의 체류시간(Residence time)을 10초 이하로 하는 것을 목표로 하고 있다. 촉매의 체류시간이 짧으면 그만큼 프로판 공급량의 주입속도 또한 빠르고, 바로 촉매가 재생되어 다시 반응에 참여하므로, 상업용 공정으로 개발될 때 프로필렌 생산량이 고정층 공정에 비해 매우 증가하게 된다. The goal of the conventionally developed FPDH process is to set the residence time of the catalyst to 10 seconds or less. When the residence time of the catalyst is short, the injection rate of the propane supply is also fast, and the catalyst is immediately regenerated and participates in the reaction again. Therefore, when developed as a commercial process, propylene production is significantly increased compared to the fixed bed process.
하지만 촉매와 프로판의 접촉시간이 그만큼 짧기 때문에 촉매의 효율이 매우 중요해진다. 즉, 촉매의 두 가지 효율 척도인 선택도와 전환율을 각각 극대화 하는 것이 중요하다.However, since the contact time between the catalyst and propane is that short, the efficiency of the catalyst becomes very important. In other words, it is important to maximize the selectivity and conversion rate, which are two measures of catalyst efficiency, respectively.
나아가, 현재 사용되고 있는 프로판 탈수소화 공정기술들은 귀금속 촉매나 비연속공정을 바탕으로 구성되어 있어, 귀금속 촉매의 과활성에 (코크생성) 의한 반응기 막힘 현상이나, 고정층 반응기 밸브 시퀀스(Sequence) 트러블 등 프로필렌 생산 운전에 어려움을 겪고 있다.Furthermore, the currently used propane dehydrogenation process technologies are based on noble metal catalysts or discontinuous processes, so propylene They are having trouble running production.
또한, 프로판 탈수소화 반응은 수소에 의한 가역반응으로 인해 열역학적으로 프로판 전환율에 제한을 가지는데, 이러한 문제를 극복하기 위하여 대부분의 공정에서는 산소, 할로겐, 황화합물, 이산화탄소, 수증기 등과 같은 외부 산화제를 사용하여 수소를 물로 전환하고 있다. In addition, the propane dehydrogenation reaction has a thermodynamic limitation on the propane conversion rate due to the reversible reaction by hydrogen. Hydrogen is being converted to water.
따라서 프로필렌의 효과적인 대량생산을 위해서는 상기 연속공정의 문제를 해결하고 산화제 없이 직접식 탈수소화 촉매를 사용함으로써 생산비용이 절감된 새로운 프로판 탈수소화 공정의 개발이 요구된다.Therefore, for effective mass production of propylene, it is required to develop a new propane dehydrogenation process in which the production cost is reduced by solving the problem of the continuous process and using a direct dehydrogenation catalyst without an oxidizing agent.
프로판 탈수소화에 사용되는 촉매 중에서 귀금속 촉매의 경우 활성점에 수소가 흡착되는 직접 탈수소화 메카니즘으로 반응이 진행되나, 전이금속 산화물의 경우 전자의 이동성으로 인한 활성점의 불완전성으로 그 메커니즘이 확실히 규명되지 못하고 있는 실정이다.Among the catalysts used for propane dehydrogenation, in the case of noble metal catalysts, the reaction proceeds with a direct dehydrogenation mechanism in which hydrogen is adsorbed to the active site, but in the case of transition metal oxides, the mechanism has been clearly identified due to the incompleteness of the active site due to electron mobility. It is currently not possible.
이러한 사정하에, 통상 PDH 촉매로 가장 많이 사용되는 촉매는 Pt-Sn, VOx, CrOx 촉매가 있다. CrOx 촉매가 프로판 전환율과 선택도 측면에서 매우 우수하지만, 환경오염 및 인체유해성 등의 문제와 문제와 반응초기 산화반응 제어의 어려움으로 인해 그 사용이 제한되고 있다. 백금촉매는 선택도는 우수하나 값이 비싸고, 코크 생성 속도가 매우 빨라 이에 대한 세밀한 제어가 요구된다. 또한 조촉매 성분인 Sn 및 다른 금속과의 결합에 따라 촉매 고유활성이 달라지며, Sn의 환경 유해성 증가로 인해 백금촉매 역시 새로운 다성분 촉매 개발이 지속적으로 요구되는 실정이다.Under these circumstances, catalysts most commonly used as PDH catalysts include Pt-Sn, VOx, and CrOx catalysts. Although the CrOx catalyst is very good in terms of propane conversion rate and selectivity, its use is limited due to problems such as environmental pollution and human harm, and difficulties in controlling the oxidation reaction in the initial stage of the reaction. The platinum catalyst has excellent selectivity, but is expensive, and the coke generation rate is very high, so precise control is required. In addition, the intrinsic activity of the catalyst varies according to the combination of Sn and other metals, which is a co-catalyst component, and the platinum catalyst is also continuously required to develop a new multi-component catalyst due to the increase in the environmental hazard of Sn.
한편, 특허문헌 1 및 2의 촉매를 포함한 종래 촉매의 경우에는 촉매의 코크 침적으로 인해 비활성화가 문제가 된다.On the other hand, in the case of the conventional catalyst including the catalyst of Patent Documents 1 and 2, deactivation becomes a problem due to coke deposition of the catalyst.
이에 본 발명자들은 지속적인 연구를 통해 신규 촉매를 도입함으로써 종래의 기술에 비해 촉매의 전환율 및 선택도가 동시에 우수한 올레핀 제조용 촉매 및 그 제조방법을 개발하였다.Accordingly, the present inventors have developed a catalyst for olefin production and a method for preparing the same, which at the same time have excellent catalyst conversion and selectivity compared to the prior art by introducing a new catalyst through continuous research.
(특허문헌 1) 한국공개특허 제2018-0079178호(Patent Document 1) Korea Patent Publication No. 2018-0079178
(특허문헌 2) 국제공개특허 WO2016/13561(Patent Document 2) International Patent Publication WO2016/13561
본 발명의 목적은 에탄, 프로판, 부탄 등 알칸족 가스로부터 올레핀을 제조하는데, 전환율 및 선택도가 우수한 올레핀 제조용 촉매 및 그 제조방법을 제공하는 데 있다.It is an object of the present invention to provide a catalyst for preparing olefins, which is excellent in conversion and selectivity, and a method for preparing olefins from alkane gases such as ethane, propane, butane, and the like.
본 발명에 따른 알칸족 가스로부터 올레핀 제조용 촉매는, 붕소를 포함하는 알루미나 담체에 금속활성성분이 담지되는 것이 바람직하다.In the catalyst for producing olefins from an alkane gas according to the present invention, it is preferable that a metal active component is supported on an alumina carrier containing boron.
상기 붕소는 알루미나 무게 대비 0.1~2 중량%로 담지되는 것이 바람직하다.The boron is preferably supported in an amount of 0.1 to 2% by weight based on the weight of alumina.
상기 붕소는 담체 무게 대비 0.5~2 중량%로 담지되는 것이 보다 바람직하다.It is more preferable that the boron is supported in an amount of 0.5 to 2% by weight based on the weight of the carrier.
상기 금속활성성분은 코발트를 필수적으로 포함하는 것이 바람직하다.It is preferable that the metal active component essentially contains cobalt.
상기 코발트는 알루미나 무게 대비 1~5 중량%로 담지되는 것이 바람직하다.The cobalt is preferably supported in an amount of 1 to 5% by weight based on the weight of alumina.
상기 금속활성성분이 백금을 추가로 포함하는 것이 보다 바람직하다.It is more preferable that the metal active component further comprises platinum.
상기 백금은 알루미나 무게 대비 0.001~0.05 중량%로 담지되는 것이 바람직하다.The platinum is preferably supported in an amount of 0.001 to 0.05 wt % based on the weight of alumina.
본 발명에 따른 알칸족 가스로부터 올레핀 제조용 촉매의 제조방법은, A method for producing a catalyst for olefin production from an alkane gas according to the present invention,
붕소 포함 용액에 알루미나를 함침하고, 소성하여, 붕소-알루미나 담체를 제공하는 단계;impregnating alumina in a boron-containing solution and calcining to provide a boron-alumina carrier;
상기 금속활성성분을 포함하는 용액을 제공하는 단계; providing a solution containing the metal active ingredient;
상기 붕소-알루미나 답체를 금속활성성분을 포함한 용액에 함침하고, 건조시키는 단계; 및 impregnating the boron-alumina solution in a solution containing a metal active ingredient, and drying; and
상기 금속활성성분이 담지된 붕소-알루미나 담체를 700℃~900℃에서 소성시키는 단계를 포함하는 것이 바람직하다.It is preferable to include the step of calcining the boron-alumina carrier on which the active metal component is supported at 700°C to 900°C.
상기 붕소-알루미나 담체는 400~600℃에서 소성되는 것이 바람직하다.The boron-alumina carrier is preferably calcined at 400 to 600 °C.
본 발명의 또다른 측면은, 본 발명에 따라 제조된 알칸족 가스로부터 올레핀 제조용 촉매를 포함하는 연속 반응-재생 올레핀 제조 방법을 제공하는 것이다. Another aspect of the present invention is to provide a process for the production of continuous reaction-regenerated olefins comprising a catalyst for the production of olefins from an alkane gas produced according to the present invention.
상기 연속 반응-재생 올레핀 제조 방법에서 반응 온도가 560~640℃인 것이 바람직하다.In the continuous reaction-regenerated olefin production method, the reaction temperature is preferably 560 to 640°C.
상기 연속 반응-재생 올레핀 제조 방법에서 원료인 알칸의 유량(WHSV)이 4~16 h-1인 것이 바람직하다.In the continuous reaction-regenerated olefin production method, it is preferable that the flow rate (WHSV) of alkane as a raw material is 4 to 16 h -1 .
본 발명에 따른 에탄, 프로판, 부탄 등 알칸족 가스로부터 올레핀 제조용 촉매 및 그 제조방법은 전환율 및 선택도가 우수하여, 고정층 반응기 및 유동층 반응기 모두에 효과적이지만, 특히 종래 상업적으로 실현되지 못한 FPDH 공정의 실현을 가능하게 한다. 특히, 본 발명에 따른 촉매는 종래 촉매들에 비해 코크 침착에 의한 촉매 비활성화 현상을 현저히 개선함으로써 높은 전환율 및 선택도를 갖는다.The catalyst for producing olefins from alkane gases such as ethane, propane, butane, and the like according to the present invention and a method for producing the same have excellent conversion and selectivity, so they are effective for both a fixed bed reactor and a fluidized bed reactor, but in particular, the FPDH process that has not been commercially realized in the prior art. make realization possible. In particular, the catalyst according to the present invention has a high conversion rate and selectivity by significantly improving catalyst deactivation by coke deposition compared to conventional catalysts.
도 1은 붕소 함량에 따른 상용 알루미나의 PDH 반응 초기(1-3초) 활성 결과를 개략적으로 도시한 것이다.1 schematically shows the results of the initial PDH reaction (1-3 seconds) of commercial alumina according to the boron content.
도 2는 4Co/Al2O3 및 4Co-0.7B/Al2O3 촉매의 PDH 활성 실험 결과를 비교하여 개략적으로 도시한 것이다.Figure 2 is a schematic diagram comparing the PDH activity experimental results of 4Co/Al 2 O 3 and 4Co-0.7B/Al 2 O 3 catalysts.
도 3은 붕소 함량에 따른 4Co-0.01Pt/Al2O3 촉매의 PDH 반응 활성 실험 결과를 개략적으로 도시한 것이다.3 schematically shows the results of the PDH reaction activity of the 4Co-0.01Pt/Al 2 O 3 catalyst according to the boron content.
도 4는 4Co-0.01Pt-x%B 촉매의 1분 PDH 반응 후 촉매 이미지를 개략적으로 도시한 것이다.Figure 4 schematically shows the catalyst image after 1 minute PDH reaction of the 4Co-0.01Pt-x%B catalyst.
도 5는 Co-Pt 촉매 및 Co-Pt-B 촉매의 PDH 초기 활성 실험결과를 비교하여 개략적으로 도시한 것이다.5 is a schematic view comparing the experimental results of the PDH initial activity of the Co-Pt catalyst and the Co-Pt-B catalyst.
도 6은 붕소의 함량에 따른 Co-Pt-B 촉매의 PDH 초기의 TOS 활성 실험 결과를 개략적으로 도시한 것이다.6 schematically shows the experimental results of TOS activity in the initial PDH of the Co-Pt-B catalyst according to the content of boron.
도 7은 4Co-0.01Pt/Al2O3 촉매 및 4Co-0.01Pt-0.7B/Al2O3 촉매의 연속 반응-재생 및 재순환 반응 활성 결과를 개략적으로 도시한 것이다.7 schematically shows the results of continuous reaction-regeneration and recycling reaction activity of a 4Co-0.01Pt/Al 2 O 3 catalyst and a 4Co-0.01Pt-0.7B/Al 2 O 3 catalyst.
도 8은 4Co-0.01Pt-0.7B/Al2O3 촉매의 연속 반응-재생 및 재순환 반응 활성의 상세 결과를 개략적으로 도시한 것이다.8 schematically shows the detailed results of the continuous reaction-regeneration and recycle reaction activity of 4Co-0.01Pt-0.7B/Al 2 O 3 catalyst.
본 발명에 따른 알칸족 가스로부터 올레핀 제조용 촉매는, 붕소를 포함하는 알루미나 담체에 금속활성성분이 담지되는 것이 바람직하다.In the catalyst for producing olefins from an alkane gas according to the present invention, it is preferable that a metal active component is supported on an alumina carrier containing boron.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시 형태를 설명한다. 그러나, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 실시예들을 설명함에 있어서, 동일 구성에 대해서는 동일 명칭 및 부호가 사용되며, 이에 따라 중복되는 부가적인 설명은 아래에서 생략된다. 아래에서 참조되는 도면들에서는 축적비가 적용되지 않는다.In describing the present embodiments, the same names and reference numerals are used for the same components, and thus overlapping additional descriptions are omitted below. In the drawings referenced below, no scale ratio applies.
본 발명에 따른 알칸족 가스로부터 올레핀 제조용 촉매는, 붕소를 포함하는 알루미나 담체에 금속활성성분이 담지되는 것이 바람직하다.In the catalyst for producing olefins from an alkane gas according to the present invention, it is preferable that a metal active component is supported on an alumina carrier containing boron.
상기 알루미나 담체는 탈수소화 반응온도 이상의 550~850℃의 제조온도에서 γ~θ 상을 갖는 것이 바람직하며, 이 범위에서 80~300 m2/g 의 표면적을 갖는다.The alumina carrier preferably has a γ to θ phase at a manufacturing temperature of 550 to 850° C. above the dehydrogenation reaction temperature, and has a surface area of 80 to 300 m 2 /g in this range.
상기 담체가 탈수소화 반응온도보다 낮은 온도에서 제조될 경우 탈수소화 반응시 촉매의 열적 변형이 일어날 수 있으며, 900℃ 초과 온도에서 제조될 경우 담체의 결정화로 인해 낮은 촉매 표면적을 가지게 되며 이는 반응물과 접촉 시 촉매활성을 위한 물질 전달을 저해하게 된다.If the carrier is prepared at a temperature lower than the dehydrogenation reaction temperature, thermal deformation of the catalyst may occur during the dehydrogenation reaction. It inhibits mass transfer for catalytic activity.
촉매에 일반적으로 사용되는 담지체인 알루미나의 산점에서 기인하는 코크(coke) 침적이 지배적이므로, 먼저 상용 알루미나 담체인 Puralox에 붕소를 0~2 중량%로 변경시켜 담지하여 PDH 반응 초기 반응 활성을 실험하였다. Since coke deposition due to the acid site of alumina, a support generally used in catalysts, is dominant, first, boron was changed to 0-2 wt% on Puralox, a commercially available alumina support, and supported to test the initial reaction activity of the PDH reaction. .
랩규모 고정층 반응기에서 실험하여, 실험 결과인 반응 초기 TOS 1-3초 사이의 값을 평균내어 도 1에 도시하였다. 반응 실험은 600℃, WHSV 16h-1 및 WHSV 4h-1 조건에서 실험하였다.The experiment was conducted in a lab-scale fixed-bed reactor, and the values between the initial TOS, which are the experimental results, between 1-3 seconds were averaged and shown in FIG. 1 . Reaction experiments were conducted at 600° C., WHSV 16h-1 and WHSV 4h-1 conditions.
주 활성점(active site)인 Co 또는 Pt 금속이 없는 알루미나만으로 유량이 WHSV 16h-1인 조건에서, 반응초기에 10% 이상의 전환율을 보였다. 또한 4배 느린 반응인 유량 WHSV 4 h-1 조건에서는 25% 이상의 전환율을 보이며, 프로필렌 생산보다는 부반응인 크래킹(cracking) 등으로 인해 메탄, 에틸렌 등의 생성 비율이 높았다.Alumina without Co or Pt metal, which is the main active site, showed a conversion rate of 10% or more at the beginning of the reaction under the condition that the flow rate was WHSV 16h-1. In addition, under the WHSV 4 h-1 condition, which is a 4 times slower reaction, a conversion rate of 25% or more was shown, and the production rate of methane and ethylene was higher than propylene production due to cracking, which is a side reaction.
이후, 알루미나에 담지된 붕소의 양이 0.2 중량%에서 1 중량%까지 증가할수록 알루미나의 활성이 급격하게 떨어지는 것이 확인되었다. 1 중량%부터 2 중량%까지 붕소의 담지량을 더욱 증가시키면, 전환율 감소는 미미해지고 선택도가 감소하는 경향을 보였다. 이것은 붕소가 알루미나의 부반응 위치를 효과적으로 억제하여, 코크 침적 및 부산물 생성을 억제할 수 있음을 의미한다. 따라서, 붕소의 함량은 알루미나 무게 대비 0.5~2 중량%가 가장 효과적일 것으로 판단된다.Thereafter, it was confirmed that as the amount of boron supported on the alumina increased from 0.2 wt% to 1 wt%, the activity of alumina rapidly decreased. When the loading amount of boron was further increased from 1 wt% to 2 wt%, the reduction in conversion was insignificant and the selectivity tended to decrease. This means that boron can effectively suppress the side reaction site of alumina, thereby suppressing coke deposition and by-product formation. Therefore, it is determined that the content of boron is most effective in 0.5 to 2% by weight based on the weight of alumina.
전통적으로 탈수소촉매를 위한 활성 금속은 다양하지만, FPDH 공정 특성인, 수초 이내의 반응 극초기에서 높은 선택도를 얻기 위해서는 코발트가 바람직하며, 나아가 코발트 기반 촉매의 고선택도 성질을 유지하면서 전환율을 향상시키기 위해 백금이 추가되는 것이 바람직하다.Traditionally, there are various active metals for dehydrogenation catalysts, but cobalt is preferable to obtain high selectivity in the very early stage of the reaction within seconds, which is characteristic of the FPDH process, and furthermore, the conversion rate is improved while maintaining the high selectivity properties of the cobalt-based catalyst. It is preferable to add platinum to make it.
상기 코발트는 알루미나 무게 대비 1~5 중량%로 담지되는 것이 바람직하다. 상기 범위를 벗어난 촉매량은 FPDH에 상업적으로 적용가능한 범위를 벗어난다. 또한, 촉매량이 많으면 결정성 산화물이 형성되기 때문에 탈수소촉매로는 부정적이다. 나아가, 상기 범위를 넘어 촉매량이 증가하면 수율이 현저히 감소하게 된다.The cobalt is preferably supported in an amount of 1 to 5% by weight based on the weight of alumina. Catalyst amounts outside the above range are outside the commercially applicable range for FPDH. In addition, since a crystalline oxide is formed when the catalyst amount is large, it is negative as a dehydrogenation catalyst. Furthermore, when the amount of catalyst is increased beyond the above range, the yield is significantly reduced.
프로판 탈수소 반응의 TOS 1-3초 내에서의 반응에서, 코발트 촉매의 경우 가장 높은 선택도를 나타내고, 전환율은 백금이 가장 크게 기여하는 것으로 보인다. 따라서, 높은 선택도를 갖는 코발트 촉매의 낮은 전환율을 백금촉매가 보완하는 것으로 추정된다.In the reaction within 1-3 seconds of TOS of the propane dehydrogenation reaction, the cobalt catalyst shows the highest selectivity, and platinum seems to contribute the most to the conversion. Therefore, it is estimated that the platinum catalyst compensates for the low conversion rate of the cobalt catalyst with high selectivity.
상기 백금의 양이 증가할수록 프로판 전환율이 증가하면서 전체 프로필렌 수율 또한 증가함을 알 수 있다. 그러나 백금의 양이 증가할수록 부반응 또한 지속적으로 증가하는데 주된 부생성물로는 메탄과 에탄이었다. 이는 백금 촉매가 탈수소 반응뿐만 아니라 생성된 수소와 프로판이 만나 메탄과 에탄을 형성하는 수소화분해(Hydrogenolysis) 반응에도 매우 높은 활성이 있음을 나타낸다.It can be seen that as the amount of platinum increases, the propane conversion rate increases and the overall propylene yield also increases. However, as the amount of platinum increases, side reactions also continuously increase, and the main by-products are methane and ethane. This indicates that the platinum catalyst has very high activity not only in the dehydrogenation reaction but also in the hydrogenolysis reaction in which the produced hydrogen and propane meet to form methane and ethane.
따라서, 백금의 도입량에 따른 전환율의 상승 구간 및 선택도의 지속적인 감소를 고려할 때, 상기 백금은 알루미나 무게 대비 0.001~0.05 중량%로 담지되는 것이 빠른 순환유동층 공정에 적용하기에 가장 적합한 촉매임을 알 수 있다.Therefore, considering the increase in the conversion rate and the continuous decrease in the selectivity according to the amount of platinum introduced, it can be seen that the platinum supported at 0.001 to 0.05 wt % relative to the weight of alumina is the most suitable catalyst for application to the fast circulating fluidized bed process. there is.
한편, 본 발명에 따른 알칸족 가스로부터 올레핀 제조용 촉매의 제조방법은, On the other hand, the method for producing a catalyst for olefin production from an alkane gas according to the present invention,
붕소 포함 용액에 알루미나를 함침하고, 소성하여, 붕소-알루미나 담체를 제공하는 단계;impregnating alumina in a boron-containing solution and calcining to provide a boron-alumina carrier;
상기 금속활성성분을 포함하는 용액을 제공하는 단계; providing a solution containing the metal active ingredient;
상기 붕소-알루미나 답체를 금속활성성분을 포함한 용액에 함침하고, 건조시키는 단계; 및 impregnating the boron-alumina solution in a solution containing a metal active ingredient, and drying; and
상기 금속활성성분이 담지된 붕소-알루미나 담체를 700℃~900℃에서 소성시키는 단계를 포함하는 것이 바람직하다.It is preferable to include the step of calcining the boron-alumina carrier on which the active metal component is supported at 700°C to 900°C.
상기 촉매는 700℃~900℃에서 소성시킨 것이 바람직하다. 촉매는 소성 온도에 따라 촉매 상(phase)이 변하는데, 상기 온도 범위 이외에서는 나노크기의 결정상을 형성하기 때문에 산화환원 반응을 주로 일으키므로 탈수소촉매로는 바람직하지 않다.The catalyst is preferably calcined at 700°C to 900°C. The catalyst phase changes depending on the calcination temperature. Outside the above temperature range, it is not preferable as a dehydrogenation catalyst because it mainly causes a redox reaction because it forms a nano-sized crystal phase.
상기 붕소-알루미나 담체는 400~600℃에서 소성되는 것이 바람직하다. 담체로 사용하기 위해서는 넓은 비표면적을 유지하는 것이 바람직하며, 상기 온도 범위보다 높을 경우 알루미나 담체의 상이 변화하여 표면적이 감소하고, 결정화가 진행될 수 있다. The boron-alumina carrier is preferably calcined at 400 to 600 °C. In order to use it as a carrier, it is preferable to maintain a large specific surface area, and when the temperature is higher than the above temperature range, the phase of the alumina carrier changes and the surface area decreases, and crystallization may proceed.
종래, 결정도가 높을 것으로 예상되는 졸겔법 및 침전법으로 합성한 촉매는 탈수소화 반응보다는 산화반응에 의한 CO2 생성이 주를 이루기 때문에 바람직하지 않다. 반면, 알루미나의 비율을 높인 합성법인 EISA법에 의한 중형기공 촉매나, 알루미나 고체 슬러리 상에서 침전법으로 합성한 촉매의 경우엔 알루미나 담지체의 산점이 적절하게 제어되어 탈수소 반응의 선택성을 높여 줄 수 있다.Conventionally, the catalyst synthesized by the sol-gel method and the precipitation method, which are expected to have high crystallinity, is not preferable because the production of CO 2 by oxidation reaction rather than dehydrogenation reaction is predominant. On the other hand, in the case of a medium pore catalyst by EISA method, a synthesis method with an increased alumina ratio, or a catalyst synthesized by a precipitation method on an alumina solid slurry, the acid point of the alumina support is appropriately controlled, thereby increasing the selectivity of the dehydrogenation reaction. .
본 발명의 또다른 측면은, 본 발명에 따라 제조된 알칸족 가스로부터 올레핀 제조용 촉매를 포함하는 연속 반응-재생 올레핀 제조 방법을 제공하는 것이다. 보다 바람직하게는, 프로판으로부터 프로필렌을 제조하는 것이다.Another aspect of the present invention is to provide a process for the production of continuous reaction-regenerated olefins comprising a catalyst for the production of olefins from an alkane gas produced according to the present invention. More preferably, propylene is produced from propane.
상기 연속 반응-재생 올레핀 제조 방법에서 반응 온도가 560~640℃인 것이 바람직하다. 탈수소반응(PDH)은 평형반응이기 때문에 높은 반응온도가 요구된다. 그러나, 640℃ 이상부터 급격하게 부반응일 일어남과 동시에, 높은 온도에 의한 열적 반응(무촉매)으로 인해 부산물이 증가한다. 따라서, 선택도 감소를 최소화 하기 위해서는 그 이상의 온도는 바람직하지 않다. In the continuous reaction-regenerated olefin production method, the reaction temperature is preferably 560 to 640°C. Since the dehydrogenation reaction (PDH) is an equilibrium reaction, a high reaction temperature is required. However, side-reactions occur rapidly from 640°C or higher, and at the same time, by-products increase due to thermal reaction (non-catalyst) caused by high temperature. Therefore, in order to minimize the decrease in selectivity, a temperature higher than that is not preferable.
또한, 반응 중 코크 침적 등을 제거하기 위해 재생이 요구되는데, 반응온도와 재생부 온도가 상호 의존적이라, 재생부는 반응온도보다 대략 20-30℃ 정도 높은 온도로 설정되게 된다. 따라서, 560℃의 반응일 경우 약 590℃ 정도로 재생부에서 코크를 제거하게 된다. 이보다 낮은 온도범위에서는 신속한 코크 제거를 통해 촉매를 재생시키는데 어려움이 있다. In addition, regeneration is required to remove coke deposition during the reaction. Since the reaction temperature and the temperature of the regeneration unit are mutually dependent, the regeneration unit is set at a temperature approximately 20-30°C higher than the reaction temperature. Therefore, in the case of a reaction at 560°C, the coke is removed from the regeneration unit at about 590°C. In a temperature range lower than this, it is difficult to regenerate the catalyst through rapid coking.
상기 연속 반응-재생 올레핀 제조 방법에서 원료인 알칸의 유량(WHSV)이 4~16 h-1인 것이 바람직하다. 보다 바람직하게는 12~16 h-1이다. 상기 범위내의 유량에서 촉매가 원활히 순환되며, 빠른 체류시간(RT)을 가질 수 있다.In the continuous reaction-regenerated olefin production method, it is preferable that the flow rate (WHSV) of alkane as a raw material is 4 to 16 h -1 . More preferably, it is 12-16 h -1 . At a flow rate within the above range, the catalyst circulates smoothly and can have a fast residence time (RT).
이하에서, 본 발명을 제조예 및 실시예를 통하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail through Preparation Examples and Examples.
<제조예><Production Example>
1. 붕소산화물-알루미나 담체 제조 (B/Alumina)1. Preparation of boron oxide-alumina support (B/Alumina)
붕소산화물-알루미나 담체 제조를 위한 붕소 전구체는 붕산(Boric acid)을 사용하였다. Boric acid was used as a boron precursor for preparing the boron oxide-alumina carrier.
금속 산화물 용액 제조를 위해 메탄올을 알루미나의 기공 부피와 같은 양으로 준비하였다. 알루미나 대비 0.2~2 중량%의 붕소(B)를 가지고 있는 H3BO3(붕산)을 준비된 메탄올에 주입 후 2시간-4시간 교반시켜 붕소 산화물 용액을 제조하였다. To prepare a metal oxide solution, methanol was prepared in an amount equal to the pore volume of alumina. H 3 BO 3 (boric acid) having 0.2 to 2% by weight of boron (B) compared to alumina was injected into the prepared methanol and stirred for 2 hours to 4 hours to prepare a boron oxide solution.
제조한 금속 산화물 용액을 알루미나에 첨가하여 초기 습윤함침법 (incipient wetness impregnation)으로 함침하였고, 분당 2℃의 승온 속도로 승온시킨 후 500℃ 소성 온도에서 6시간동안 소성하여 붕소산화물-알루미나 담체를 제조하였다.The prepared metal oxide solution was added to alumina, impregnated by incipient wetness impregnation, and the temperature was raised at a rate of 2° C. per minute, and then calcined at a firing temperature of 500° C. for 6 hours to prepare a boron oxide-alumina carrier. did.
2. 공침법을 통한 코발트/붕소산화물-알루미나 촉매 제조 2. Preparation of cobalt/boron oxide-alumina catalyst through co-precipitation
(Co/B-Alumina)(Co/B-Alumina)
금속 산화물 용액 제조를 위해 물을 알루미나 기공 부피와 같은 양으로 준비하였다. 알루미나 대비 0~10 중량%의 코발트를 포함하고 있는 Co(NO3)2·6H2O (질산코발트6수화물)을 물에 교반시켜 용액을 제조하였다.To prepare a metal oxide solution, water was prepared in an amount equal to the alumina pore volume. Co(NO 3 ) 2 .6H 2 O (cobalt nitrate hexahydrate) containing 0 to 10% by weight of cobalt relative to alumina was stirred in water to prepare a solution.
상기 제조한 금속산화물 용액을 상기 제조된 붕소산화물-알루미나에 첨가하여 초기습윤합침법 (incipient wetness impregnation)으로 함침하였고, 50~75℃에서 12시간 건조해준 뒤, 분당 1℃의 승온 속도로 승온시켜 700℃~900℃ 소성 온도에서 6시간동안 소성하여 각각 코발트/붕소산화물-알루미나 촉매를 제조하였다.The prepared metal oxide solution was added to the prepared boron oxide-alumina, impregnated by incipient wetness impregnation, dried at 50 to 75° C. for 12 hours, and then heated at a temperature increase rate of 1° C. per minute. Each of the cobalt/boron oxide-alumina catalysts was prepared by calcination at a calcination temperature of 700° C. to 900° C. for 6 hours.
3. 공침법을 통한 코발트-백금/붕소산화물-알루미나 촉매 제조 3. Preparation of cobalt-platinum/boron oxide-alumina catalyst through co-precipitation
(Co-Pt/B-Alumina)(Co-Pt/B-Alumina)
금속 산화물 용액 제조를 위해 물을 알루미나 기공 부피와 같은 양으로 준비하였다. 알루미나 대비 0~10 중량%의 코발트를 포함하고 있는 Co(NO3)2·6H2O (질산코발트6수화물) 및 0~200ppm (0~0.02 중량%)의 백금을 가지고 있는 H2PtCl6·xH2O (염화백금산)을 공침(co-impregnation)하여 코발트-백금 산화물 용액을 제조하였다.To prepare the metal oxide solution, water was prepared in an amount equal to the alumina pore volume. Co(NO 3 ) 2 6H 2 O (cobalt nitrate hexahydrate) containing 0 to 10% by weight of cobalt compared to alumina and H 2 PtCl 6 containing 0 to 200ppm (0 to 0.02% by weight) of platinum xH 2 O (chloroplatinic acid) was co-impregnation to prepare a cobalt-platinum oxide solution.
상기 제조한 금속산화물 용액을 상기 제조된 붕소산화물-알루미나에 첨가하여 초기습윤합침법 (incipient wetness impregnation)으로 함침하였고, 50~75℃에서 12시간 건조해준 뒤, 분당 1℃의 승온 속도로 승온시킨 후 700℃~900℃ 소성 온도에서 6시간동안 소성하여 각각 코발트-백금/붕소산화물-알루미나 촉매를 제조하였다.The prepared metal oxide solution was added to the prepared boron oxide-alumina and impregnated by incipient wetness impregnation, dried at 50 to 75° C. for 12 hours, and then heated at a temperature increase rate of 1° C. per minute. After calcining at a calcination temperature of 700° C. to 900° C. for 6 hours, each cobalt-platinum/boron oxide-alumina catalyst was prepared.
<연속 반응 재생 실험방법 (Recycle Test) 및 활성 평가><Continuous reaction regeneration test method (Recycle Test) and activity evaluation>
연속 반응 재생을 위해 설비된 자동 연속 반응 시스템을 사용하여 고정층(Fixed-bed) 형태의 반응기에 제조된 촉매를 주입 후, 불활성 가스인 질소 가스 분위기에서 반응 및 재생 온도인 600℃까지 분당 10℃의 승온속도로 도달하였다. 반응기가 600℃에 도달한 후, 연속 반응 재생 실험을 수행하였다. 5분 동안 100 mL/min 질소로 반응기에 흘려 준 뒤, 30초 동안 50 mL/min 50%프로판/50%질소 혼합가스로 환원을 하였다. 다시 5분 동안 질소로 반응기에 흘린 후, 9분 30초 동안 100 mL/min 의 공기 분위기에서 재생 과정을 거쳤다. 이를 한 번의 반응 재생 실험으로 하여, 1~1000 회 연속 재생을 수행하였다.After injecting the prepared catalyst into a fixed-bed type reactor using an automatic continuous reaction system equipped for continuous reaction regeneration, the reaction and regeneration temperature of 10 °C per minute is increased in an inert gas nitrogen gas atmosphere to 600 °C. The temperature rise rate was reached. After the reactor reached 600° C., a continuous reaction regeneration experiment was performed. After flowing into the reactor at 100 mL/min nitrogen for 5 minutes, reduction was performed with a 50 mL/min 50% propane/50% nitrogen mixed gas for 30 seconds. After flowing into the reactor with nitrogen for 5 minutes again, the regeneration process was performed in an air atmosphere of 100 mL/min for 9 minutes and 30 seconds. This was used as one reaction regeneration experiment, and continuous regeneration was performed 1 to 1000 times.
연속 반응 재생기에서 촉매를 회수하여 고정층(Fixed-bed) 형태의 반응기에 0.4 g의 제조된 촉매를 주입 후, 불활성 가스인 헬륨 가스 분위기에서 반응 및 재생 온도인 600℃까지 분당 10℃의 승온속도로 도달하였다. 이후 16 초 동안 105 mL/min 50%프로판/50%질소 혼합가스로 환원을 하였고, 30 mL/min 의 공기 분위기에서 재생 과정을 거쳤다. 다음으로, 헬륨 가스를 이용하여 반응기 및 촉매에 흡착된 산소를 20 분 동안 제거 후, 50 % 프로판/질소 혼합가스를 105 mL/min 유량으로 주입하여 16h-1의 WHSV로 반응이 수행되었다. 16포트 밸브에 매 초마다 반응 결과물을 수집하여, 가스크로마토그래피를 통해 분석되었다.After recovering the catalyst from the continuous reaction regenerator and injecting 0.4 g of the prepared catalyst into a fixed-bed type reactor, the reaction and regeneration temperature is 600° C. reached. After that, it was reduced with a mixed gas of 105 mL/min 50% propane/50% nitrogen for 16 seconds, and the regeneration process was performed in an air atmosphere of 30 mL/min. Next, after removing oxygen adsorbed to the reactor and the catalyst for 20 minutes using helium gas, a 50% propane/nitrogen mixed gas was injected at a flow rate of 105 mL/min, and the reaction was performed with a WHSV of 16h -1 . The reaction result was collected every second in the 16-port valve and analyzed by gas chromatography.
상기에서 제조된 촉매의 반응 활성을 실험한 결과를 도 1 내지 도 8에 개략적으로 도시하였다.The results of testing the reaction activity of the catalyst prepared above are schematically shown in FIGS. 1 to 8 .
먼저, 백금을 제외한 Co 촉매에도 붕소의 효과가 있는지 확인해 본 결과, 도 2에 도시한 바와 같이, 전환율 및 선택도가 모두 개선됨을 알 수 있었다. 4 중량%의 Co 촉매의 경우 약 22% 전환율 및 97%의 선택도를 보였고, 0.7 중량%의 붕소가 첨가되면 전환율은 34%로 증가하고 선택도는 99%로 더욱 우수한 활성을 보였다. 특히 WHSV 8 h-1 조건인 체류시간(RT: retention time)이 2배 증가한 경우, 전환율은 47%로 증가하였고 선택도는 99%로 개선 효과가 크게 증가하였다. 결국, 백금이 없는 촉매인 4Co-0.7B 촉매도 공정의 반응조건을 통해 순환 유동층 PDH 공정 촉매로서 적합할 것으로 기대된다.First, as a result of checking whether boron has an effect on the Co catalyst except for platinum, it was found that both the conversion rate and the selectivity were improved, as shown in FIG. 2 . In the case of 4 wt% of Co catalyst, about 22% conversion and 97% selectivity were exhibited, and when 0.7 wt% of boron was added, the conversion increased to 34% and the selectivity was 99%, showing better activity. In particular, when the retention time (RT: retention time) of WHSV 8 h-1 was doubled, the conversion rate increased to 47% and the selectivity increased to 99%, which greatly improved the improvement effect. After all, it is expected that the platinum-free catalyst, 4Co-0.7B, will also be suitable as a catalyst for the circulating fluidized bed PDH process through the reaction conditions of the process.
또한, 종래 개발된 4 중량%의 Co와 0.01 중량%의 Pt가 혼합된 4Co-0.01Pt/Al2O3 촉매의 붕소 함량에 따른 효과를 실험하였다. 담체는 상용 Puralox 알루미나 담체를 사용하였고, 붕소의 함량을 0~2 중량%까지 증가시켜 촉매를 제조한 후, PDH 초기 활성 분석을 수행하였다. 반응 실험은 온도 600℃, 유량 WHSV 16h-1 및 WHSV 4h-1 조건에서 실험하였다. 도 3은 반응 초기 1-3초의 전환율 및 선택도의 평균값을 도시한 것이다.In addition, the effect according to the boron content of the conventionally developed 4Co-0.01Pt/Al 2 O 3 catalyst in which 4 wt% of Co and 0.01 wt% of Pt are mixed was tested. A commercially available Puralox alumina carrier was used as the carrier, and the catalyst was prepared by increasing the boron content to 0 to 2 wt%, and then PDH initial activity analysis was performed. The reaction experiment was conducted at a temperature of 600° C. and a flow rate of WHSV 16h-1 and WHSV 4h-1. Figure 3 shows the average values of the conversion and selectivity in the initial stage of the reaction 1-3 seconds.
붕소의 함량이 증가할수록 프로필렌 선택도는 지속적으로 증가함을 알 수 있었다. 유량 WHSV 16 h-1 조건에서, 4Co-0.01Pt 촉매의 선택도는 약 95% 였으나, 붕소가 0.7~2 중량%로 추가로 담지된 촉매에서는 99% 이상의 프로필렌 선택도를 나타내었다. 프로판 전환율은 0.2 중량%의 붕소가 담지될 경우 47%에서 43%로 소폭 감소하였으나, 붕소의 함량 0.5~2 중량%로 증가시킬 경우 53%까지 증가하는 것을 알 수 있었다. 이후 더 많은 양의 붕소가 담지되면서 전환율이 서서히 감소하였다. As the content of boron increased, it was found that the propylene selectivity increased continuously. Under the flow rate WHSV 16 h-1 condition, the selectivity of the 4Co-0.01Pt catalyst was about 95%, but the catalyst in which boron was additionally supported in an amount of 0.7 to 2 wt% showed a selectivity of 99% or more to propylene. The propane conversion rate was slightly decreased from 47% to 43% when 0.2 wt% of boron was supported, but it was found that it increased to 53% when the boron content was increased to 0.5 to 2 wt%. Afterwards, as a larger amount of boron was loaded, the conversion rate was gradually decreased.
한편, 유량 WHSV 4 h-1 조건에서, 4Co-0.01Pt 촉매의 프로필렌 선택도는 약 85% 수준이었으나, 붕소의 함량이 증가하면서 97%의 선택도로 급격히 증가하였다. 프로판 전환율 또한 지속적으로 소폭 상승하는 결과를 보였다.On the other hand, under the WHSV 4 h-1 flow rate condition, the selectivity to propylene of the 4Co-0.01Pt catalyst was about 85%, but the selectivity to 97% was sharply increased as the content of boron increased. The propane conversion rate also showed a result of continuously increasing slightly.
도 4는 1분 동안 PDH 반응을 거친 후 촉매의 색상을 비교하여 나타내었다. Co-Pt 촉매 (0B)는 빠른 코크 침적으로 인해 원래의 코발트 블루 색에서 검정색으로 변하였다. 붕소의 함량에 따른 반응 후 촉매의 이미지를 보면, 붕소의 함량이 증가할수록 원래의 촉매 색상인 코발트 블루색을 그대로 유지하고 있었다. 4 shows the color comparison of the catalyst after the PDH reaction for 1 minute. The Co-Pt catalyst (0B) changed from its original cobalt blue color to black due to rapid coke deposition. Looking at the image of the catalyst after the reaction according to the content of boron, as the content of boron increased, the original color of the catalyst, cobalt blue, was maintained.
결론적으로 PDH 반응 결과와 사용 후 촉매의 이미지를 보면, 붕소 첨가 후 99% 정도의 프로필렌 선택도를 보이는 고선택성 촉매가 제조되었고, 이에 따라 부반응의 경로가 차단되면서 코크 침적이 매우 억제되었음을 알 수 있었다.In conclusion, looking at the PDH reaction result and the image of the catalyst after use, a high selectivity catalyst showing 99% propylene selectivity after boron addition was prepared, and as a result, the path of side reaction was blocked and coke deposition was very suppressed. .
또한, 0.7 중량%의 붕소가 첨가된 촉매와 첨가되지 않은 촉매의 PDH 반응 활성을 비교하여 보았다. 스팀 처리 후의 안정성과 체류시간(Retention time)이 길어짐에 따른 부반응 증가 현상을 함께 비교하기 위하여, 반응은 600℃의 동일한 온도에서 수행하면서, 유량을 WHSV: 4 h-1 및 16h-1로, 그리고 스팀 처리 후 촉매를 동시에 비교한 결과를 도 4에 나타내었다.In addition, the PDH reaction activity of the catalyst to which 0.7 wt% of boron was added and the catalyst not to which boron was added was compared. In order to compare the stability after steam treatment and the increase in side reactions as the retention time is increased, the reaction is carried out at the same temperature of 600 °C, and the flow rate is WHSV: 4 h-1 and 16h-1, and The results of simultaneous comparison of catalysts after steam treatment are shown in FIG. 4 .
결과적으로, 붕소 첨가 후, 전환율과 선택도 모두 개선되었으며, 특히 WHSV 4h-1 조건에서는 붕소의 부반응 차단 효과가 두드러지게 확인되었다.As a result, after the addition of boron, both the conversion rate and the selectivity were improved, and in particular, the side reaction blocking effect of boron was remarkably confirmed under the WHSV 4h-1 condition.
또한, 도 6에는 붕소의 함량에 따른 Co-Pt-B 촉매의 유량 WHSV 16 h-1에서의 활성 실험 결과를 나타내었다. 붕소를 포함하는 촉매 모두가 전환율과 선택도가 크게 개선됨을 알 수 있었다.In addition, FIG. 6 shows the results of the activity experiment at the flow rate WHSV 16 h-1 of the Co-Pt-B catalyst according to the content of boron. It was found that all of the catalysts including boron significantly improved conversion and selectivity.
또한, 도 7에는 4Co-0.01Pt/Al2O3 촉매 및 4Co-0.01Pt-0.7B/Al2O3 촉매의 연속 반응-재생 및 재순환 반응 활성 결과를 비교하여 나타내었다. 1000회 정도 재순환 실험 결과, 붕소 첨가 후에도 촉매 안정성에는 문제가 없었고, 전환율/선택도 모두 붕소 첨가 전보다 개선됨을 알 수 있었다.In addition, FIG. 7 shows a comparison of the results of continuous reaction-regeneration and recycle reaction activity of the 4Co-0.01Pt/Al 2 O 3 catalyst and the 4Co-0.01Pt-0.7B/Al 2 O 3 catalyst. As a result of the recycle experiment about 1000 times, it was found that there was no problem in catalyst stability even after the addition of boron, and both the conversion and selectivity were improved compared to before the addition of boron.
보다 구체적으로 도 8에 도시된 바와 같이, 4Co-0.01Pt-0.7B/Al2O3 촉매의 연속 반응-재생 및 재순환 반응 활성의 상세 결과를 살펴보면, 수율도 안정적이고, 부반응 억제 효과가 지속적으로 우수함을 알 수 있었다.More specifically, as shown in Figure 8, the continuous reaction of the 4Co-0.01Pt-0.7B/Al 2 O 3 catalyst - Looking at the detailed results of the regeneration and recycle reaction activity, the yield is also stable, and the side reaction inhibitory effect is continuously was found to be excellent.
이는 반응공정에 따라 같은 탈수소 촉매 금속성분이라 할지라도, 최적의 조합촉매 구성 및 담지량에 의해 그 효과가 달라짐을 나타낸다. FPDH 공정에서 필요한 백금의 양은 무빙베드 형태의 공정에서 필요로 하는 양보다 극히 적은 양으로도 효과가 우수하며, 프로필렌 선택도 또한 코발트와 붕소의 도입으로 인해 크게 향상되었다.This indicates that even with the same metal component of the dehydrogenation catalyst depending on the reaction process, the effect is different depending on the optimal composition and loading amount of the combined catalyst. The amount of platinum required in the FPDH process is excellent even in an amount that is extremely small compared to the amount required in the moving bed type process, and the propylene selectivity is also greatly improved due to the introduction of cobalt and boron.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만, 이러한 실시예는 예시적인 것으로서 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, these embodiments are exemplary and the scope of the present invention is not limited thereto, and various modifications are made within the scope not departing from the technical spirit of the present invention described in the claims. And it will be apparent to those of ordinary skill in the art that modifications are possible.
본 발명은 에탄, 프로판, 부탄 등 알칸족 가스로부터 올레핀을 제조하는데, 종래 기술에 비해 선택도 및 전환율이 향상된 올레핀 제조용 촉매 및 그 제조방법에 관한 것이다.The present invention relates to a catalyst for producing olefins with improved selectivity and conversion compared to the prior art for producing olefins from alkane gases such as ethane, propane, and butane, and a method for producing the same.

Claims (18)

  1. 붕소를 포함하는 알루미나 담체에 금속활성성분이 담지된, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.A dehydrogenation catalyst for producing olefins from an alkane gas, in which a metal active component is supported on an alumina carrier containing boron.
  2. 제 1 항에 있어서, 상기 붕소가 알루미나 무게 대비 0.1~2 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.The dehydrogenation catalyst for producing an olefin from an alkane gas according to claim 1, wherein the boron is supported in an amount of 0.1 to 2 wt% based on the weight of alumina.
  3. 제 2 항에 있어서, 상기 붕소가 담체 무게 대비 0.5~2 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.The dehydrogenation catalyst for producing an olefin from an alkane gas according to claim 2, wherein the boron is supported in an amount of 0.5 to 2 wt% based on the weight of the carrier.
  4. 제 1 항에 있어서, 상기 금속활성성분이 코발트를 필수적으로 포함하는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.The dehydrogenation catalyst for producing olefins from an alkane gas according to claim 1, wherein the metal active component essentially comprises cobalt.
  5. 제 4 항에 있어서, 상기 코발트가 알루미나 무게 대비 1~5 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.The dehydrogenation catalyst for producing olefins from an alkane gas according to claim 4, wherein the cobalt is supported in an amount of 1 to 5% by weight based on the weight of alumina.
  6. 제 4 항에 있어서, 상기 금속활성성분이 백금을 추가로 포함하는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.The dehydrogenation catalyst for producing an olefin from an alkane gas according to claim 4, wherein the metal active component further comprises platinum.
  7. 제 6 항에 있어서, 상기 백금이 알루미나 무게 대비 0.001~0.05 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매.The dehydrogenation catalyst for producing an olefin from an alkane gas according to claim 6, wherein the platinum is supported in an amount of 0.001 to 0.05 wt% based on the weight of alumina.
  8. 붕소 포함 용액에 알루미나를 함침하고, 소성하여, 붕소-알루미나 담체를 제공하는 단계;impregnating alumina in a boron-containing solution and calcining to provide a boron-alumina carrier;
    상기 금속활성성분을 포함하는 용액을 제공하는 단계; providing a solution containing the metal active ingredient;
    상기 붕소-알루미나 답체를 금속활성성분을 포함한 용액에 함침하고, 건조시키는 단계; 및 impregnating the boron-alumina solution in a solution containing a metal active ingredient, and drying; and
    상기 금속활성성분이 담지된 붕소-알루미나 담체를 700℃~900℃에서 소성시키는 단계를 포함하는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.A method for producing a dehydrogenation catalyst for producing olefins from an alkane gas, comprising calcining the boron-alumina carrier on which the metal active component is supported at 700° C. to 900° C.
  9. 제 8 항에 있어서, 상기 붕소-알루미나 담체가 400~600℃에서 소성되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.[Claim 9] The method of claim 8, wherein the boron-alumina carrier is calcined at 400 to 600°C.
  10. 제 8 항에 있어서, 상기 붕소가 알루미나 무게 대비 0.1~2 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.The method of claim 8, wherein the boron is supported in an amount of 0.1 to 2 wt% based on the weight of alumina, and the dehydrogenation catalyst for producing olefins from an alkane gas.
  11. 제 10 항에 있어서, 상기 붕소가 담체 무게 대비 0.5~2 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.11. The method of claim 10, wherein the boron is supported in an amount of 0.5 to 2 wt% based on the weight of the carrier, the method for producing a dehydrogenation catalyst for producing olefins from an alkane gas.
  12. 제 8 항에 있어서, 상기 금속활성성분이 코발트를 필수적으로 포함하는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.The method of claim 8, wherein the metal active component essentially contains cobalt.
  13. 제 12 항에 있어서, 상기 코발트가 알루미나 무게 대비 1~5 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.13. The method of claim 12, wherein the cobalt is supported in an amount of 1 to 5 wt% based on the weight of alumina, the method for producing a dehydrogenation catalyst for producing olefins from an alkane gas.
  14. 제 12 항에 있어서, 상기 금속활성성분이 백금을 추가로 포함하는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.13. The method of claim 12, wherein the metal active component further comprises platinum.
  15. 제 14 항에 있어서, 상기 백금이 알루미나 무게 대비 0.001~0.05 중량%로 담지되는, 알칸족 가스로부터 올레핀을 제조하기 위한 탈수소촉매의 제조방법.15. The method of claim 14, wherein the platinum is supported in an amount of 0.001 to 0.05 wt% based on the weight of alumina, the method for producing a dehydrogenation catalyst for producing olefins from an alkane gas.
  16. 제 1 항의 촉매를 포함하는 연속 반응-재생 올레핀 제조 방법. A process for the production of continuous reaction-regenerated olefins comprising the catalyst of claim 1.
  17. 제 16 항에 있어서, 상기 반응 온도가 560~640℃인 연속 반응-재생 올레핀 제조 방법.17. The method according to claim 16, wherein the reaction temperature is 560 to 640 °C.
  18. 제 16 항에 있어서, 상기 올레핀 제조 방법에서 원료인 알칸의 유량(WHSV)이 4~16 h-1인 연속 반응-재생 올레핀 제조 방법.The method according to claim 16, wherein the flow rate (WHSV) of an alkane as a raw material in the olefin production method is 4 to 16 h -1 .
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